Production of colored photographic images



3,012,884- PRODUCTION @F COLGRED PHOTOGIHC WAGES The present inventionrelates to a method of producing colored photographic images, moreparticularly such images which are free from unwanted secondary imagesdue to undesired absorptions of the dyestuffs.

It is known that by color development a dyestuif image is formed whichmostly shows an undesirable side-absorption and that it can becompensated by a mask image of opposite gradation and with an absorptionto compensate the undesirable absorption all over the layer.

One means to do this is the use in the emulsion layer of a colored colorcoupler with a suitable absorption but losing it Where color developmenttakes place, so that afterwards the remaining color couplerautomatically forms the desired masking. The filter action of thiscolored color coupler in the emulsion inevitably involves a loss ofsensitivity.

Another means to obtain the desired mask image consists in converting,after color development, the residue of the color coupler into a coloredcompound with adequate absorption. This often requires supplementarybaths and has in no case given satisfactory results.

It is an object of the present invention to provide a method ofobtaining masked images without using colored color couplers. It is afurther object of the present invention to provide a method of obtainingmasked images without special treatments, at least if the substancesadded to the photographic material have been rendered fast to diffusion.Further objects of the present invention will appear from the followingdescription.

These objects are accomplished by color development of a multilayermaterial containing color couplers and subsequent treatment with anoxidizing substance in the presence of a compound which after oxidationcouples with one of the color couplers.

The oxidizing substance can be present in a special bath or in one ofthe baths normally used. Preferably, the oxidizing substance normallypresent in the bleaching bath is used.

The mask-forming compound can be present in a bath between the colordeveloper and the bleaching bath, or in one of the sensitive ornon-sensitive layers of the photographic material. It may beadvantageous that it be fast to difiusion and preferably it correspondsto the following general formula:

I Rs

wherein R =hydrogen or any substituent, e.g. alkyl including aralkyl,aryl, carboxyl including esterified carboxyl or amino including acylamino;

R =alky1 including aralkyl, aryl, or a heterocyclic residue;

ice

2 R =hydrogen, alkyl including aralkyl, aryl, acyl, i.e. all

the radicals which can be obtained by withdrawing a hydroxyl group froman acid, or a heterocyclic residue.

It is possible of course to use derivatives of these substances whereinthe amino group is substituted by a group which inhibits neither theoxidation nor the coupling.

Mask-forming compounds are for instance:

(I 4-amino-antipyrine 0r 1-phenyl-2:3-dimethyl-4- amino-pyrazolone-S (2)1,2dfphenyl-3-melhyl-4-amin0-pyrazolone-5 This product can be preparedaccording to A. Heymans, Ber. 66 (1933), 1654/61.

(3) 2-phenyl-3-methyl-4-amin0-pyraz0I0ne-5 This product can be preparedas follows: 8.7 g. of 1- phenyl-4-phenylazo-S-methyl-pyrazolone-3,prepared according to Michaelis, Ber. 38, 155 and Ann. 338, 228, arereduced in cm. of dioxane in the presence of Raney nickel as catalyst.After elimination of the catalyst by filtration, evaporation ofthe'solvent to dryness, and washing with ether, 4.1 g. of an amine,melting at 180 C., are obtained. After purification over the benzalcompound as described by Michaelis, Ann. 350, 295, an amine, melting at182 C., is obtained.

(4) 1-benzoyl-2-pheny[-3-methyl-4-amin0-pyrazolone-5- hydrachloride Thisproduct can be prepared as follows: to 27.8 g. of1-phenyl-4-phenylazo-5-methyl-pyrazolone-3 (described by Michaelis asabove) dissolved in 100 om. of dioxane, 22 cm. of benzoylchlon'de and300 cm. of an aqueous solution of sodium hydroxide 5 N are addedsimultaneously and drop by drop at 10 C. The oil formed is washed withan aqueous solution of sodium hydroxide N until solidification and theproduct is sucked off, washed with Water, then with ethanol, andrecrystallized from ethanol. 29.6 g. of a product, melting at 127 C.,are obtained.

9.5 g. of the above compound are dissolved in 70 cm. of ethyl acetateand hydrogenated in the presence of palladium as catalyst. Afterelimination of the catalyst by filtration, the hydrochloride of theamine is precipitated by means of etheric hydrogen chloride. 8 g. of aproduct which after recrystallization from methyl ethylketone melts at160 C. (with decomposition) are obtained.

(5) 1-phenylsulphonyl-Z-phenyl-3-methyl-4-amin0-pyrraz0l0ne-5-hydr0chl0ride This product can be obtained as follows: asolution of 18 g. of 1-phenyl-4-phenylazo-5-methyl-pyrazolone-3(described by Michaelis as before) in 60 cm. of dioxane is addedsimultaneously and drop by drop with 28 cm. of benzene sulphochloride to250 cm. of an aqueous solution of sodium hydroxide N at a temperature of25-30 C. The precipitate formed is sucked off and washed with water.After recrystallization from ethanol, 21 g. of a product, melting at 132C. are obtained.

11 g. of this azo compound are hydrogenated in 150 cm? of ethylacetatein the presence of Raney nickel as catalyst at about 50 C. Afterevaporation of the solvent, treatment with etheric hydrogen chloride andrecrystallization from acetonitrile, 7.5 g. of a product, melting at C.(with decomposition), are obtained.

(6) I -phenyZ-2-hexadecyl-3-methyl-4-amino-pyraz0lone-5 This product canbe obtained as follows: 174 g. of 1- phenyl-3-methyl-pyrazolone-5 and500 g. of cetyltoluenesulphonate are melted for 3 h. at 160 C.- The oilobtained is boiled with n-hexane, dissolved in ether and shaken out withsodium hydroxide solution in order to remove unaltered pyrazolone. Afterevaporation of the ether, the residue is dissolved in 1300 cm. ofdioxane and after addition of 150 cm. of water and 95 cm. ofconcentrated hydrochloric acid nitrosated at 10 C. by means of asolution of 40 g. of sodium nitrite in 275 cm. of water. After thirtyminutes extra stirring, the green precipitate is centrifuged and Washedwith water and subsequently with methanol. 70 g. of a product, meltingat 160 C. (with decomposition), are obtained.

8.5 g. of the nitroso compound in 150 cm. of ethyl acetate arehydrogenated in the presence of Raney nickel as catalyst. Afterfiltration, the amine is precipitated from the solution in the form ofsulphate by addition of 1 cm. of concentrated sulphuric acid. Aftersucking off, the sulphate is Washed with ether. 6.2 g. of a product,melting at 150 C. (with decomposition), are obtained. The free base isobtained by dissolving the sulphate in ethanol and completelyprecipitating the product with water. This base after recrystallizationfrom cyclohexane melts at 124 C.

(7) 2 [p- (a-hexadecenyI-succinyZ-amido)-phenyl] -3-marhyl-4-amino-pyraz0l0ne-5 This product can be obtained as follows: to20 g. of alpha-acetyl-beta-(p-nitrphenyl)hydrazine and 14 g. of acetylacetic acid ethyl ester, 15 cm. of phosphorus trichloride are addedwhilst stirring at between 0 and 5 C. The mixture is slowly brought toroom temperature and then gradually heated to 70 C. When the developmentof hydrogen chloride is practically finished and the reaction mass hasbecome viscous and stiff, it is dissolved in acetic acid and neutralizedwith an aqueous solution of sodium carbonate. The sucked off product iswashed with water. After drying, 20 g. of a product, melting above 260C., and which can be recrystallized from acetonitrile or from xylene areobtained.

18.4 g. of this 1-p-nitrophenyl-5-methyl-pyrazolone-3 are hydrogenatedin methyl Cellosolve in the presence of Raney nickel as catalyst. Afterelimination of the catalyst by filtration, the solvent is evaporated.The solid residue is Washed with ether and recrystallized fromacetontrile. 13 g. of a product, melting at 220 C., are obtained.

5.7 g. of 1-paminophenyl-5-methyl-pyrazolone-3 are refluxed for 3 h.with 9.7 g. of hexadecenyl succinic acid anhydride in methylethylketone,and after evaporation of the solvent to dryness and recrystallizationfrom acetonitrile, 12.2 g. of a product, melting at 117 C., areobtained.

3.24 g. of dichloroaniline are diazotized in 8 cm. of concentratedsulphuric acid and 20 cm. of water at 0 C. with a solution of 1.6 g. ofsodium nitrite in 5 cm. of water. The diazoniurn solution obtained isadded drop by drop at 5 C. to 10.22 g. of the foregoing compounddissolved in an aqueous solution of sodium carbonate 10%. The mixture isacidified with acetic acid, the precipitate obtained is washed withwater and recrystallized from ethanol. 8.6 g. of a product, meltingat142 C., are obtained.

1 g. of the azo compound thus obtained is hydrogenated in methylCellosolve in the presence of palladium as catalyst. After filtering,pouring out into water, sucking off and washing with acetonitrile, 0.8g. of a product, melting at 170 C. is obtained.

phenyl-3pentadecyl-pyrazolone-S and 93 g. of methylp-toluenesulphonateare melted together for 30 h. at

4 140 C. In order to remove the toluenesulphonic acid formed thereaction mixture is fixed together with an aqueous sodium hydroxidesolution 5%. After extraction with ether and recrystallization fromn-hexane, 99 g. of 1-phenyl-2-methyl-3-pentadecyl-pyrazolone-5 areobtained. Yield: 61%. Melting point: 65 C.

99 g. of the above compound are dissolved in acetic acid, cooled down to10 C. and nitrosated by dropwise addition of a solution of 20 g. ofsodium nitrite in 50 cm. of water Whilst thoroughly stirring with anUltra Turrax stirrer. The reaction liquid changes into a mass which isfurther stirred for 15 minutes. After dropwise adding 400 cm. of water,sucking off, washing with water until all acid is removed, drying andrecrystallizing from xylene at a temperature not higher than 70, 54.5 g.of 1-phenyl-2 methyl-3-pentadecyl-4-nitroso-pyrazolone-5 are obtained.Yield: 51%. Melting point: C.

80 g. of the above nitroso compound are hydrogenated in 900 cm. ofmethanol at 40 C. in the presence of Raney nickel as catalyst. Afterfiltration and evaporation of the solvent, the oily residue is coveredwith 60 cm. of chloroformic acid ethyl ester. After about 2 h., thereaction mass has solidified. After washing with ether andcrystallization from n-hexane, 49 g. of l-phenyl- 2methyl-3-pentadecyl-4-carbethoxyamino-pyrazolone-5 are obtained. Yield:62%. Melting point: 65 C.

(9) 1 -phenyl-2-methyl-3- ma-lzexadecenybsucciny lumido plzelzyl]-4-amin0pyraz0l0n 8-5 This product can be obtained as follows: 562 g. of1- phenyl-3-m-nitrophenyl pyrazolone-S and 560 g. of methyl-p-toluenesulphonate are melted together for 20 h. at C. The cooled reaction massis dissolved in chloroform and the solution is washed with an aqueoussodium carbonate solution 5% in order to split off toluene sulphonicacid. After recrystallization from ethanol, 388 g. ofl-phenyl-2-metbyl-3-rn-nitrophenylpyrazolone-S are obtained. Yield: 66%.Melting point: 224 C.

383 g. of the latter nitro compound, dissolved in 2.5 l. of methylCellosolve are hydrogenated at 60 C. in the presence of Raney nickel ascatalyst. After eliminating the catalyst by filtration, the solution isevaporated to dryness and the residue is crystallized from n-butanol.255 g. of 1-phenyl-2-methyl-3-m-aminophenyl-pyra2olone-5 are obtained.Yield: 74%. Melting point: 222 C.

40 g. of the above amine and 48 g. of alpha-hexadecenyl succinic acidanhydride are refluxed for 1 /2 h. in 1.5 l. of acetonitrile. Theprecipitate which is produced on cooling is first washed with ethylacetate and then crystallized from the same solvent. 43 g. of1-phenyl-2-methyl-3- [m-(alpha-hexadecenyl succinyl) amido]-phenyl-pyrazolone-5 are obtained. Yield: 49%.

14.5 g. of the above compound are dissolved in cm? of acetic acid. Afteradding 36 cm. of concentrated hydrochloric acid the solution isnitrosated with 21 cm. of an aqueous sodium nitrite solution 20% atabout 5 C. After 20 minutes further stirring, the solution is poured outinto water and the green nitroso compound formed is sucked off. Thelatter is dis-solved in 450 cm? of ethanol and hydrogenated at 35 C. inthe presence of Raney nickel as catalyst. After sucking off thecatalyst, the solution is evaporated to dryness and the remainingresidue is thoroughly washed with acetonitrile. 6 g. of 1 phenyl2-methyl-3-{m-(alpha-hexadecenyl-succinyl)- amido]-phenyl 4amino-pyrazolone 5 are obtained. Yield: 41%. Melting point: 140 C. (withdecomposition).

(10) Methyl ester of I-(p-succinyl-amido)-phenyZ-2-methyl-3-penJadecyl-4-amino-pyraz0lone-5 This product can be obtained asfollows: 382 g. of pnitrophenyl hydrazine and 164 g. of palmitoyl aceticacid off with a part of the isopropanol. After sucking off andcrystallizing from ethanol, 850 g. of 1-p-nitr0phenyl-3-pentadecyl-pyrazolone-S are obtained. Yield: 82%. Melting point: 111 C.

519 g. of the above pyrazolone are melted together with 256 g. ofmethyl-p-toluene sulphonate at 135-140 C. for 30 h. After cooling, thereaction mass is dissolved in about 2.5 l. of chloroform. This solutionis shaken with an about 5% aqueous sodium carbonate solution in order tosplit off the toluene sulphonic acid from the quaternary salt, washedwith water until the wash water is neutral and the chloroform solutionis evaporated to dryness, and after recrystallization from petroleumsolvent, 421 g. of 1-p-nitrophenyl-2-rnethyl-3- pentadecyl-pyrazolone-Sare obtained. Yield: 78%. Melting point: 78 C.

121 g. of the above nitroso compound are hydrogenated in 1250 cm. ofmethyl Cellosolve at 60 C. in the presence of Raney nickel as catalyst,the latter is eliminated by filtration and the solvent is evaporated todryness. After recrystallization from acetonitrile, 108 g. ofl-pamino-phenyl-2-methyl-3-pentadecyl-pyrazolone-5 are obtained. Yield:95%. Melting point: 104 C.

40 g. of this amine are dissolved in 400 cm. of warm acetonitrile and 15g. of beta-carbomethoxy-propionyl chloride are added in portions. Thesolution is refluxed for 10 minutes and after cooling, the product issucked oif in order to complete the crystallization and recrystallizedfrom acetonitrile. 44 g. of 1-[p-( beta-carbomethoxy propionyl)amino]phenyl-2-methyl-3-pentadecyl-pyrazolone-S are obtained. Yield: 86%.Melting point: 159 C.

40 g. of this compound are dissolved in 400 cm of ethylene chlorohydrineand the temperature of the solution is brought at 15 C. 11 cm. ofconcentrated hydrochloric acid solution and next, dropwise Whilststirring at 10-15 C., 60 cm. of an aqueous sodium nitrite solution 20%are added. After 1 to 1 /2 h. stirring, 600 cm. of water are added.Stirring is continued for another 1 h. in order to obtain a morecrystalline and filtrable pre cipitate. After sucking E, thoroughlywashing with water and crystallizing from ethanol, 25.5 g. of1-[p-(beta-carb0- methoxy propionyl) amido]phenyl-2-methyl-S-pentadecyl-4-nitroso pyrazolone-S are obtained. Yield:60%.

48 g. of this nitroso compound in a mixture of 850 cm. of ethanol and 70cm. of concentrated hydrochloric acid solution are reduced at 30-35 C.with zinc powder until the solution is colorless. The zinc is eliminatedby filtration and the filtrate is added whilst stirring to 1 /2 1. ofsaturated aqueous sodium acetate solution. After sucking off, washingwith water and recrystallizing from ethyl acetate and subsequently fromacetonitrile, 28 g. of l-[pbeta-carbomethoxy-propionyl)amido]-phenyl-2-rnethyl-3- pentadecyl-4-amino pyrazolone-S are obtained.Yield: 59%. Melting point: 163 C.

(11 1 -phenyl-2-( -sulph0)-pr0pyl-3-pentadecyl-4-acetylamid0-pyraz0l0ne-5 This product can beobtained as follows: a diazonium salt solution prepared from 90 cm. ofaniline is dropwise added to 222 g. of1-phenyl-3-pentadecyl-pyrazolonein 250 cm. of an aqueous sodiumhydroxide solution N. After /2 h. stirring the solution is neutralizedwith about 30 cm. of acetic acid. After sucking ofi the precipitateobtained, washing with water and crystallizing from acetic acid, 220 g.of 1-phenyl-3-pentadecyl4-phen ylazo-pyrazolone-S are obtained. Yield:77%. Melting point 99 C.

95 g. of this azo compound are dissolved in warm state in a mixture of600 cm. of acetic acid and 300 cm. of acetic anhydride and whilst thesolution is still warm zinc powder is added until the liquid isdecolorized. After 1 /2 h. refluxing, the solution is poured into ice.After sucking off the precipitated compound and recrystallizing frompetroleum solvent, 33 g. of 1-phenyl-3-pentadecyl-4- 6diacetylamino-pyrazolone-5 are obtained. Yield; 38%. Melting point: 107C.

14 g. of this compound are heated for 30 h. at C. with 8 g. of n-propanesultone. After cooling, washing with ether and crystallizing fromdioxane, 12 g. of 1-phenyl-2-( gamma-sulpho) -propyl-3-pentadecyl-4-acetylamino-pyrazolone-S are obtained. Yield: 65%. Byrecrystallization from acetonitrile the melting point can be increasedto 180 C.

By boiling this compound for 2 min. in Water the acetylamino issaponified to a free amino group. The solution thus obtained is added tothe photographic emulsion.

(12) 1 -phenyl-2-methyl3- [p- (ot-hexadecenyl-succinyl) amido]-benz0ylamid0-4-amin0-pyraz0l0ne-5 This product can be obtained asfollows: 33 g. of finely divided 1 phenyl 2 methyl-3-amino-pyrazolone-5(prepared according to H. Stenzl, Helv., 33 (1950) 1189); are suspendedin cm. of acetone and Whilst stirring 105 cm. of a 40% aqueous sodiumhydroxide solution and 65 g. of p-nitrobenzoylchloride in 105 cm. ofacetone are simultaneously and dropwise added at 0 C. After furtherstirring for 1 h., 1 l. of water is added and the suspension is filteredand the filtrate is acidified with acetic acid. After sucking off theprecipitate, washing with water and then with acetone and crystallizingfrom methyl Cellosolve, 47 g. of 1phenyl-2-methyl-3-p-nitrobenzoylamino-pyrazolone-5 are obtained. Yield:80%. Melting point: above 260 C.

70 g. of this nitro compound are hydrogenated at 75 in 2 1. of methylCellosolve in the presence of Raney nickel as catalyst. Afterconcentrating and recrystallizing the formed crystals from methylCellosolve, 56 g. of 1-phenyl-2-rnethyl-3-p-aminobenzoylaminopyrazolone-S are obtained. Yield: 88%. Melting point: 222 C.

18.6 g. of this compound and 21.6 g. of alpha-hexadecenyl succinic acidanhydride are refluxed for 3 h. 700 cm. of acetonitrile. Afterevaporating the acetonitrile and crystallizing from ethyl acetate, 21 g.of l-phenyl-Z- methyl 3 [-p-(alpha-hexadecenylsuccinyl)amido]-benzoyl-amino-pyrazolone-S are obtained. Yield: 55%.Melting point: 190 C. (with decomposition).

11 g. of this compound are dissolved in cold state in 20 cm? of anaqueous sodium carbonate solution 2 N. To this solution is added atbetween 0 and 5 C. a solution of p-chlorophenyl diazonium sulphateprepared from 23.5 g. of p-chloroaniline. The precipitated yellowazodyestuif is washed with water and dried and 12.5 g. of

1-phenyl-2-methyl 3 -'[p (alpha-hexadecenyl-succinyl)-amido]-benzoyl-amino 4 (p-chloro)phenylazo-pyrazolone-5 are obtained.Yield: 90%. Melting point: 185 C. By recrystallization from ethanol themelting point can be brought to 186 C., however with considerable loss.

4 g. of the above azo compound are dissolved in 60 cm. of ethanol. Afteradding 6 cm. of concentrated hydrochloric acid solution, the solution isreduced at 45 C. by adding zinc powder until the dyestulf isdecolorized. After filtration, the filtrate is poured out into asolution of 16 g. of sodium acetate in'100 cmfi of water, sucked off,Washed with water and then with acetonitrile, and 3 g. of 1phenyl-2-methyl-3-[p-(alpha-hexadecenyl-succinyl)- amido] benzoyl amino4 amino-pyrazolone-S are obtained. Yield: 92%. Melting point: about C.(with decomposition).

Hereinafter follow some examples which illustrate our invention Withoutlimiting, however, the scope thereof:

EXAIVIPLE 1 A strip of negative multilayer material, the underlyingred-sensitive layer of which contains l-hydroxy-Z- naphthoic acidhexadecylarnide-4-sulphonic acid as color coupler is exposed to a wedgethrough a red-filter. This exposed film is successively: color developedin a devel- I oper containing N:N diethyl para phenylenediamine, fixed,rinsed, treated for 2 minutes in a bath composed of:

Water to 1000 cm rinsed, fixed, rinsed and dried. The area which shouldhave been white it not subjected to antipyrine treatment, is stronglyred colored. If the image of the wedge is measured behind intense red,green and blue filters, it appears that when the red filter densitiesincrease, the green filter densities decrease somewhat and the bluefilter densities increase much less than with a test strip which was nottreated with the amino antipyrine bath.

EXAMPLE 2 A film support is coated with an emulsion layer which besidestheusual red sensitizer and l-hydroxy-Z-naphthoicacid-hexadecylamide-4-sulphonic acid as color coupler also contains2-(p-alpha-hexadecenyl-succinyl-imidophenyl)-3-1nethyl-4-aminopyrazolone-5. A strip or" this film is exposed througha wedge and after color development, fixed, rinsed, bleached in the samebath as in Example 1, fixed, rinsed and dried. On measurement, adecrease of the greenand blue-filter densities is observed for anincrease of the red-filter densities, not observed in a test stripcontaining no pyrazolone derivative.

EXAMPLE 3 A film support is coated with an emulsion layer which besidesa green sensitizer and 4-hexadecenyl-succinylimido-indazolone as colorcoupler also contains 2-(p-hexadecenylsuccinylimidophenyl)-3-methyl-4-amino pyrazolone-5. After exposure of a strip as in Example1, color development, fixing, rinsing, bleaching for instance in a bathmentioned in Example 1, again fixing, rinsing and drying, at strongyellow-brown color is observed all over the surface. On measurement ofthe wedge, a much greater proportion of green to blue-filter densitythan in a comparable material coated without the pyrazolone derivativeis observed.

We claim:

1. Method of forming a color corrected image in a photographic elementhaving superposed silver halide emulsion layers sensitive to difierentregions of the visible spectrum, at least one of said layers containinga color coupler for color development, which is reactive with theoxidation product of an aromatic amino developing agent to form by colordevelopment a primary dye image which absorbs a major proportion oflight in one region of the visible spectrum, and undesirably absorbs aminor proportion of light in at least one other region of the visiblespectrum, which method comprises exposing said layers to light,developing at least said one layer containing said color coupler bycolor development with an aromatic amino developing agent, whereby saidprimary image is formed in the developed areas by coupling, leaving inthe undeveloped areas of at least said one layer residual color coupler,treating said photo- 8 graphic element with a solution containing a4-amino-S pyrazolon'e derivative of the formula wherein R is a memberselected from the group con sisting of alkyl, phenyl, and benzoylamido,R is a member selected from the group consisting of alkyl, phenyl, andp-(ot-hexadecenyl-succinyl-amido)-phenyl, R is a member selected fromthe group consisting of hydrogen, phenyl, andp-(succinyl-amido-methylester)-phenyl, and R is a member selected fromthe group consisting of hydrogen, carbethoxy, and acetyl, and treatingat least said one layer containing said residual color coupler with ableaching bath, the latter treatment resulting in the oxidation of said4-amino-5-pyrazolone derivative, whereby said secondary dye image isformed by coupling of the oxidized 4amino-5-pyrazolone derivative withsaid residual color coupler.

2. Method of forming a color corrected image in a photographic elementhaving superposed silver halide emulsion layers sensitive to differentregions of the visi ble spectrum, at least one of saidlayers containinga color coupler for color development, which is reactive with theoxidation product of an aromatic amino developing agent to form by colordevelopment a primary dye image which absorbs a major proportion oflight in one region of the visible spectrum, and undesirably absorbs aminor proportion of light in at least one other region of the visiblespectrum, at least said one layer also containing a 4-amino-5-pyrazolonederivative of the formula wherein R is a member selected from the groupconsisting of alkyl, phenyl, and benzoylamido, R is a member selectedfrom the group consisting of alkyl, phenyl, andp-(whexadeeenyl-succinyl-amido)-phenyl, R is a member selected from thegroup consisting of hydrogen, phenyl, andp-(succinyl-amido-methylester)-phenyl, and R is a member selected fromthe group consisting of hydrogen, carbethoxy, and acetyl, said colorcoupler being also reactive with the oxidation product of said 4-amino-S-pyrazolone derivative to form a secondary dye image having agradation opposite to that of said primary dye image, and absorbinglight in at least one of said unwanted minor absorption regions buttransmitting substantially all the light in said major absorptionregion, which method comprises exposing said layers to light, developingat least said one layer containing said color coupler by colordevelopment with an aromatic amino developing agent, whereby saidprimary dye image is formed in the developed areas by coupling, leavingin the undeveloped areas of at least said one layer residual colorcoupler, and treating at least said one layer containing said residualcolor coupler with a bleaching bath, said treatment resulting in theoxidation of said 4-amino- 5-pyrazolone derivative, whereby saidsecondary dye image is formed by coupling of the oxidized 4-amino-5-pyrazolone derivative with said residual color coupler.

3. Photographic element having superposed silver halide emulsion layerssensitive to different regions of the visible spectrum, at least one ofsaid layers containing a color coupler for color development, which isreactive with the oxidation product of an aromatic amino developingagent to form by color development a primary dye image which absorbs amajor proportion of light in one region of the visible spectrum, andundesirably absorbs a minor proportion of light in at least one otherregion of the visible spectrum, at least said one layer also containinga 4-amino-5-pyrazolone derivative of the formula l Ra wherein R is amember selected from the group consisting of alkyl, phenyl, andbenzoylamido, R is a member selected from the group consisting of alkyl,phenyl, and p-(a-hexadecenyl-succinyl-amido)-phenyl, R is a memberselected from the group consisting of hydrogen, phenyl, andp-(succinyl-amido-methylester)-phenyl, and R is a member selected fromthe group consisting of hydrogen, carbethoxy, and acetyl, said colorcoupler being also reactive with the oxidation product of said 4-amino-5-pyrazolone derivative to form a secondary dye image having a gradationopposite to that of said primary dye image, and absorbing light in atleast one of said unwanted minor absorption regions but transmittingsubstantially all the light in said major absorption region.

References Cited in the file of this patent UNITED STATES PATENTS2,163,781 Eggert et a1. June 27, 1939 FOREIGN PATENTS 685,061 GreatBritain Dec. 31, 1952 765,286 Great Britain Jan. 9, 1957

1. METHOD OF FORMING A COLOR CORRECTED IMAGE IN A PHOTOGRAPHIC ELEMENT HAVING SUPERPOSED SILVER HALIDE EMULSION LAYERS SENSITIVE TO DIFFERENT REGIONS OF THE VISIBLE SPECTRUM, AT LEAST ONE OF SAID LAYERS CONTAINING A COLOR COUPLER FOR COLOR DEVELOPMENT, WHICH IS REACTIVE WITH THE OXIDATION PRODUCT OF AN AROMATIC AMINO DEVELOPING AGENT TO FORM BY COLOR DEVELOPMENT A PRIMARY DYE IMAGE WHICH ABSORBS A MAJOR PROPORTION OF LIGHT IN ONE REGION OF THE VISIBLE SPECTRUM, AND UNDESIRABLY ABSORBS A MINOR PROPORTION OF LIGHT IN AT LEAST ONE OTHER REGION OF THE VISIBLE SPECTRUM, WHICH METHOD COMPRISES EXPOSING SAID LAYERS TO LIGHT, DEVELOPING AT LEAST SAID ONE LAYER CONTAINING SAID COLOR COUPLER BY COLOR DEVELOPMENT WITH AN AROMATIC AMINO DEVELOPING AGENT, WHEREBY SAID PRIMARY IMAGE IS FORMED IN THE DEVELOPED AREAS BY COUPLING, LEAVING IN THE UNDERVELOPED AREAS OF AT LEAST SAID ONE LAYER RESIDUAL COLOR COUPLER, TREATING SAID PHOTOGRAHIC ELEMENT WITH A SOLUTION CONTAINING A 4-AMINO-5PYRAZOLIEN DERIVATIVES OF THE FORMULA 